Syntheses of polyethers and biodegradable polyesters utilizing aluminium-based catalysts

Zhang, Fei 2021. Syntheses of polyethers and biodegradable polyesters utilizing aluminium-based catalysts. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

Four aluminium-based complexes have been synthesized, of which one is previously reported complex but with different crystal structure and not tested with catalysis, and three are complexes have not seen published records yet. These aluminium-based complexes are tested as catalysts for ring-opening copolymerization between cyclic anhydrides and epoxides, and for selfpolymerization of epoxides. This thesis consists of six chapters listed below: Chapter 1 is a general introduction about the syntheses of polyesters via ringopening copolymerization, syntheses of polyether through homopolymerization of epoxides and their mechanistic illustrations when metal-based catalysts were used. Several previously reported examples of metal-based catalyst for biodegradable polyester syntheses were given. Discussions about why bio-degradable polyesters are needed, why aluminium was chosen as the central metal ion for desired catalysts are also included. Chapter 2 contains details of ligand synthesis, complex synthesis of [(CpHO)2Al2Me4] (complex 1) and its characterizations via NMR and single crystal X-Ray diffraction (SCXRD). Chapter 3 provides information regarding polyester syntheses through epoxide/anhydride Ring-Opening Co-Polymerization (ROCOP) catalyzed by complex 1. Chapter 4 contains information of catalytic performances of complexes 1 for epoxide homopolymerization and discussion around the results. . Chapter 5 provides catalytic performances of complex 1 for ε-caprolactone homopolymerization and the discussions about the results. iii Chapter 6 provides details of syntheses of aminoquinoline-aluminium complexes [(AQ)2AlMe] (complex 2), [(AQ)2AlCl] (complex 3), and [(AQMe)2AlCl] (complex 4). Their catalytic performances in cyclic anhydride / epoxide Ring-Opening CoPolymerization (ROCOP) were included. Mechanistic elucidations and discussions were included. Chapter 7 contains full experimental records and full characterizations of all ligands and complexes, as well as the experimental methods for catalyzed polymer syntheses and polymer isolation/purification. Chapter 8 briefly summarizes all the works, research and conclusions of this thesis

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Chemistry
Date of First Compliant Deposit:	4 November 2021
Last Modified:	04 Nov 2022 02:30
URI:	https://orca.cardiff.ac.uk/id/eprint/145292

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